Diaminothiophenes

ABSTRACT

Diaminothiophenes of the formula ##STR1## or tautomers thereof, where R 1  and R 2  are each hydrogen or together are ##STR2##  where T 1  is hydrogen, alkyl or phenyl, T 2  and T 3  are, independently of one another, alkyl or phenyl, or T 2  and T 3  together with the nitrogen linking them are a heterocyclic radical, 
     R 3  is substituted amino and 
     R 4  is alkanoyl, benzoyl, cyano, nitro or ##STR3##  where T 4  is hydrogen, alkyl or phenyl and T 5  is the radical of a primary amine or of an active methylene compound, 
     are prepared as described. The present diaminothiophene compound is useful in the synthesis of dyes, crop protection agents and pharmaceuticals.

The present invention relates to novel diaminothiophenes of the formula I ##STR4## or tautomers thereof, where R¹ and R² are each hydrogen or together are ##STR5## where T¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, and T² and T³ are identical or different and each, independently of one another, is C₁ -C₄ -alkyl, C₅ -C₇ -cycloalkyl or phenyl or T² and T³ together with the nitrogen linking them are a 5- to 7-membered saturated heterocyclic radical which can contain further hetero atoms,

R³ is C₁ -C₂₀ -mono- or dialkylamino, C₂ -C₁₀ -mono- or dialkylamino whose alkyl is substituted and/or interrupted by one or more oxygens, C₃ -C₈ -cycloalkylamino, adamantylamino, C₂ -C₁₂ -mono- or dialkenylamino, C₃ -C₁₂ -alkynylamino, N-(C₁ -C₅ -alkyl)-N-phenylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino, hexamethyleneimino, 1-imidazolyl, 1-pyrazolyl, substituted or unsubstituted phenylamino, pyridylamino, thienylamino, hydrazino, C₁ -C₄ -mono- or dialkylhydrazino or phenylhydrazino and

R⁴ is C₁ -C₆ -alkanoyl, benzoyl, cyano, nitro or ##STR6## where T⁴ is hydrogen, C₁ -C₄ -alkyl or phenyl, and T⁵ is the radical of an active methylene compound, or hydroxyimino or N-X where X is C₁ -C₂₀ -alkyl which can be substituted and/or interrupted by one or more oxygens, substituted or unsubstituted C₃ -C₆ -alkenyl, substituted or unsubstituted C₃ -C₆ -alkynyl, substituted or unsubstituted C₃ -C₁₀ -cycloalkyl, substituted or unsubstituted phenyl, pyridyl, C₁ -C₄ -alkoxycarbonylmethyl, amino, C₁ -C₄ -dialkylamino or phenylamino.

2,4-Diaminothiophene derivatives which have a substituted amino in position 2 and an unsubstituted amino in position 4 have been disclosed (see, for 10 example, J. Prakt. Chem. 326 (1986) 459 to 464; J. Chem. Soc. Perkin Trans. I (1986) 1171 to 1179 or Monatsh. Chem. 112 (1981) 1391 to 1404). Furthermore, CH-A 583,224 describes the preparation of 2,4-diamino-3,5-dicyanothiophene. The said diaminothiophenes are, however, not especially suitable diazo components for the preparation of azo dyes.

The object of the present invention was to prepare novel diaminothiophenes which have an unsubstituted amino in position 2 and a substituted amino in position 4.

In accordance with this, we have found the diaminothiophenes of the formula I defined above.

All the alkyls and alkenyls in the abovementioned formula I can be both straight-chain and branched.

When alkyls which are interrupted by one or more oxygens occur in the formula I, they are preferably interrupted by 1 to 3, in particular 1 or 2, oxygens.

Examples of suitable substituents for phenyls in the formula I are C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, in particular chlorine or bromine, nitro, hydroxyl, amino, C₁ -C₄ -dialkylamino, carboxyl or C₁ -C₄ -alkanoyl.

Examples of suitable substituents for alkyls in the formula I are C₁ -C₅ -alkylthio, substituted or unsubstituted phenoxy, halogen, in particular chlorine or bromine, hydroxyl, amino, C₁ -C₄ -mono- or dialkylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino, C₁ -C₅ -alkoxycarbonyl or substituted or unsubstituted phenyl.

Examples of suitable substituents for alkenyls, alkynyls or cycloalkyls in the formula I are fluorine, chlorine or bromine.

When T² and T³ together with the nitrogen linking them are a 5- to 7-membered saturated heterocyclic radical which can contain further hetero atoms, suitable examples are pyrrolidino, piperidino, morpholino, thiomorpholino, thiomorpholino S,S-dioxide, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino.

Examples of T¹, T², T³ and T⁴ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

Examples of R⁴ are formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl or hexanoyl.

(The names isooctyl, isononyl, isodecyl and isotridecyl used hereinafter are trivial names derived from the alcohols obtained in the oxo synthesis (cf. Ullmanns Encyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436.)

--NX is derived from primary amines of the formula H₂ NX. Examples of these which may be mentioned are methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, neopentylamine, hexylamine, heptylamine, n-octylamine, isooctylamine, 2-ethylhexylamine, nonylamine, isononylamine, decylamine, isodecylamine, undecylamine, dodecylamine, tridecylamine, isotridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, allylamine, methallylamine, propargylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclononylamine, cyclodecylamine, 2-hydroxyethylamine, 2-methoxyethylamine,2-ethoxyethylamine,3-hydroxypropylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(2-phenoxyethoxy)propylamine, 3-benzyloxypropylamine, 2-(N,N-dimethylamino)ethylamine, 2-(N,N-diethylamino)ethylamine, 3-(N,N-dimethylamino)propylamine, 3-(N,N-diethylamino)propylamine, benzylamine, 2-phenylethylamine, 3-phenylpropylamine, aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, 2-chloroaniline, 3-chloroaniline, 3-nitroaniline, 4-nitroaniline, o-toluidine, m-toluidine, p-toluidine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, glycine methyl ester, glycine ethyl ester, glycine propyl ester, glycine butyl ester, hydrazine, N,N-dimethylhydrazine or phenylhydrazine.

T⁵ is derived from, for example, active methylene compounds of the formula H₂ T⁵. Compounds of this type have, for example, the formula ##STR7## where Z is cyano, nitro, C₁ -C₆ -alkanoyl, benzoyl, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl, carbamoyl or C₁ -C₄ -mono- or dialkylcarbamoyl, or the formulae ##STR8##

Examples of some particularly important compounds are: ##STR9##

Examples of R³ are methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, pentylamino, isopentylamino, neopentylamino, hexylamino, heptylamino, octylamino, isooctylamino, 2-ethylhexylamino, nonylamino, isononylamino, decylamino, isodecylamino, undecylamino, dodecylamino, tridecylamino, isotridecylamino, tetradecylamino, pentadecylamino, hexadecylamino, heptadecylamino, octadecylamino, nonadecylamino, eicosylamino, allylamino, propargylamino, methallylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, cyclononylamino, cyclodecylamino, 2-hydroxyethylamino, 2-methoxyethylamino, 2-ethoxyethylamino, 2-benzyloxyethylamino, 3-hydroxypropylamino, 3-methoxypropylamino, 3-ethoxypropylamino, 3-(2-phenoxyethoxy)propylamino, 3-benzyloxypropylamino, 2-aminoethylamino, 2-(N,N-dimethylamino)ethylamino, 2-(N,N-diethylamino)ethylamino, 3-(N,N-dimethylamino)propylamino, 3-(N,N-diethylamino)propylamino, benzylamino, 2-phenylethylamino, 1-phenylethylamino, phenylamino, 2-hydroxyphenylamino, 3-hydroxyphenylamino, 4-hydroxyphenylamino, 2-methoxyphenylamino, 3-methoxyphenylamino, 4-methoxyphenylamino, 2-ethoxyphenylamino, 3-ethoxyphenylamino,4-ethoxyphenylamino,2-chlorophenylamino, 3-chlorophenylamino, 4-chlorophenylamino, 2-nitrophenylamino, 3-nitrophenylamino, 4-nitrophenylamino, 2-aminophenylamino, 3-aminophenylamino, 4-aminophenylamino, 2-methylphenylamino, 3-methylphenylamino, 4-methylphenylamino, 2-ethylphenylamino, 3-ethylphenylamino, 4-ethylphenylamino, 2-pyridylamino, 3-pyridylamino, 4-pyridylamino, methoxycarbonylmethylamino, ethoxycarbonylmethylamino, propoxycarbonylmethylamino, butoxycarbonylmethylamino, 2-methoxycarbonylmethylamino, 2-ethoxycarbonylmethylamino, 2-propoxycarbonylmethylamino, 2-butoxycarbonylmethylamino, 2-(3,4-dichlorophenyl)ethylamino, 2-(3-chloro-2-methylphenyl)ethylamino, 2-(3,4-dimethoxyphenyl)ethylamino, 2-(2-chlorophenyl)ethylamino, 2-thienylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, diallylamino, N-methyl-N-butylamino, N-methyl-N-phenylamino, N-methyl-N-benzylamino, N-ethyl-N-benzylamino, 3-morpholinopropylamino, 2-(1-piperazinyl)ethylamino, phenoxyethylamino, phenoxypropylamino, 2-methylthioethylamino, 3-methylthiopropylamino, 2-ethylthioethylamino, 3-ethylthiopropylamino, 2-aminoethylamino, 3-aminopropylamino, 2-dimethylaminoethylamino, 3-dimethylaminopropylamino, 2-diethylaminoethylamino, 3-diethylaminopropylamino, diethanolamino, N-ethyl-N-phenylamino, dibenzylamino, N-methylpiperazino, 2-pyrrolidinoethylamino, 2-piperidinoethylamino, 2-morpholinoethylamino, 2-thiomorpholinoethylamino, 2-hexamethyleneiminoethylamino, 2-(N-methylpiperazino)ethylamino, hydrazino, N-methylhydrazino, N-ethylhydrazino, phenylhydrazino, N,N-dimethylhydrazino, N,N-diethylhydrazino, N,N'-dimethylhydrazino, N,N'-diethylhydrazino, N,N-dipropylhydrazino, N,N-dibutylhydrazino, 1-imidazolyl, 1-pyrazolyl, 2,4-dimethylphenylamino, 3-dimethylaminophenylamino, 4-cyanophenylamino, 2-carboxyphenylamino, 4-acetylphenylamino or 2,4-dichlorophenylamino.

Preferred diaminothiophenes of the formula I are those in which

R¹ and R² are each hydrogen or together are ##STR10## where T¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, and T² and T³ are, independently of one another, C₁ -C₄ -alkyl or phenyl, or together with the nitrogen linking them are pyrrolidino, piperidino, morpholino, thiomorpholino, piperazino, N-(C₁ -C₄ -alkyl)piperazino or hexamethyleneimino, and R³ and R⁴ each have the abovementioned meanings.

Particularly preferred diaminothiophenes of the formula I are those in which R¹ and R² are each hydrogen or together are ##STR11## where T¹ is hydrogen and T² and T³ are, independently of one another, C₁ -C₄ -alkyl.

Further particularly preferred diaminothiophenes of the formula I are those in which

R⁴ is formyl, acetyl, propionyl, butyryl, benzoyl, cyano, nitro or ##STR12## where T⁴ is hydrogen, methyl, ethyl or phenyl, and T⁵ has the abovementioned meaning.

Further particularly preferred diaminothiophenes of the formula I are those in which R³ is C₁ -C₆ -mono- or dialkylamino, allylamino, methallylamino, propargylamino, C₂ -C₆ -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or C₁ -C₄ -mono- or dialkylamino or interrupted by an oxygen, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C₁ -C₄ -alkyl)piperazino.

Further particularly preferred diaminothiophenes of the formula I are those in which R⁴ is cyano, nitro, formyl or ##STR13## where Z is cyano, nitro or C₁ -C₄ -alkoxycarbonyl.

Especially important are diaminothiophenes of the formula I in which R¹ and R² are each hydrogen or together are ═CH--N(CH₃)₂.

Very particularly important are diaminothiophenes of the formula Ia ##STR14## or tautomers thereof, where L¹ is amino,

L² is C₁ -C₆ -mono- or dialkylamino, allylamino, methallylamino, propargylamino, C₂ -C₆ -alkylamino which is substituted by phenyl, hydroxyl, phenoxy, amino or C₁ -C₄ -mono- or dialkylamino or interrupted by an oxygen, or phenylamino, pyrrolidino, piperidino, morpholino, piperazino or N-(C₁ -C₄ -alkyl)piperazino and

L³ is cyano, nitro, formyl or ##STR15## where Z is cyano, nitro or C₁ -C₄ -alkoxycarbonyl.

The diaminothiophenes of the formula I according to the invention can be obtained, for example, by reaction of aminothiophenes of the formula II ##STR16## where R¹, R² and R⁴ each has the abovementioned meaning, and Hal is chlorine or bromine, with an amino compound of the formula III

    R.sup.3 --H                                                (III)

where R³ has the abovementioned meaning.

This entails, for example, the aminothiophene II being reacted with the amino compound III in an inert solvent (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric trisamide, 1,3-dimethylimidazolin-2-one, 1,3-dimethylhexylhydropyrimidin-2-one or 1,2-diethoxyethane) at from -10° to +150° C. The molar ratio II:III is usually 1:2 to 1:10.

The aminothiophenes of the formula II have been disclosed, for example, in EP-A 193,885 or can be obtained by methods similar to those detailed therein.

The novel diaminothiophenes are valuable intermediates for the synthesis of dyes, crop protection agents or pharmaceuticals. They are especially used as diazo components (R¹ and R² =H) for the preparation of azo dyes.

The Examples which follow are intended to illustrate the invention in detail.

EXAMPLE 1 2-Amino-3,5-dicyano-4-piperidinothiophene

4,6 g of 2-amino-4-chloro-3,5-dicyanothiophene were dissolved in 25 ml of N,N-dimethylformamide (DMF). 5.3 g of piperidine were added dropwise to this at room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was then stirred into 800 g of water. The precipitate was filtered off with suction, washed with water and dried in an oven at 50° C. 5.4 g (93% of theory) of the compound of the formula ##STR17## were obtained with melting point 183° to 184° C. The NMR, IR, UV and mass spectra and the elemental analysis are consistent with the structure indicated above.

The compounds listed in the following table are obtained in a similar manner.

    __________________________________________________________________________      ##STR18##                                                                     Ex.                                               Melting                      No. Y.sup.1    Y.sup.2           Y.sup.3          point                        __________________________________________________________________________                                                       [°C.]                 2   NH.sub.2   NHCH.sub.3        CN                                            3   NH.sub.2   NHC.sub.2 H.sub.5 CN                                            4   NH.sub.2   NH-n-C.sub.3 H.sub.7                                                                             CN               177-180                      5   NH.sub.2   NH-iso-C.sub.3 H.sub.7                                                                           CN               170-171                      6   NH.sub.2   NH-n-C.sub.4 H.sub.9                                                                             CN               211-212                      7   NH.sub.2   NH-sec-C.sub.4 H.sub.9                                                                           CN               121-126                      8   NH.sub.2   NH-iso-C.sub.4 H.sub.9                                                                           CN               178                          9   NH.sub.2   NH-tert-C.sub.4 H.sub.9                                                                          CN               139-142                      10  NH.sub.2   NH-n-C.sub.5 H.sub.11                                                                            CN               177-178                      11  NH.sub.2   NH-iso-C.sub.5 H.sub.11                                                                          CN                                            12  NH.sub.2   NH-neo-C.sub.5 H.sub.11                                                                          CN                                            13  NH.sub.2   NH-n-C.sub.6 H.sub.13                                                                            CN                                            14  NH.sub.2   NH-n-C.sub.7 H.sub.15                                                                            CN               92-97                        15  NH.sub.2   NH-n-C.sub.8 H.sub.17                                                                            CN                                            16  NH.sub.2   NH-n-C.sub.9 H.sub.19                                                                            CN                                            17  NH.sub.2   NH-n-C.sub.10 H.sub.21                                                                           CN                                            18  NH.sub.2   NH-n-C.sub.11 H.sub.23                                                                           CN                                            19  NH.sub.2   NH-n-C.sub.12 H.sub.25                                                                           CN                                            20  NH.sub.2   NH-n-C.sub.13 H.sub.27                                                                           CN                                            21  NH.sub.2   NH-n-C.sub.14 H.sub.29                                                                           CN                                            22  NH.sub.2   NH-n-C.sub.15 H.sub.31                                                                           CN                                            23  NH.sub.2   NH-n-C.sub.16 H.sub.33                                                                           CN                                            24  NH.sub.2   NH-n-C.sub.17 H.sub.35                                                                           CN                                            25  NH.sub.2   NH-n-C.sub.18 H.sub.37                                                                           CN                                            26  NH.sub.2   NH-n-C.sub.19 H.sub.39                                                                           CN                                            27  NH.sub.2   NH-n-C.sub.20 H.sub.41                                                                           CN                                            28  NH.sub.2   NHCH.sub.2CHCH.sub.2                                                                             CN                                            29  NH.sub.2   NHCH.sub.2CCH     CN                                            30  NH.sub.2   NHCH.sub.2CHCHCH.sub.3                                                                           CN                                            31  NH.sub.2   NHCH.sub.2CH.sub.2OH                                                                             CN               170                          32  NH.sub.2   NHCH.sub.2CH.sub.2OCH.sub.3                                                                      CN                                            33  NH.sub.2   NHCH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                               CN               175                          34  NH.sub.2   NHCH.sub.2CH.sub.2O-nC.sub.3 H.sub.7                                                             CN                                            35  NH.sub.2   NHCH.sub.2CH.sub.2OC.sub.6 H.sub.5                                                               CN                                            36  NH.sub.2   NHCH.sub.2CH.sub.2OCH.sub.2C.sub.6 H.sub.5                                                       CN                                            37  NH.sub.2   NH CH.sub.2CH.sub.2NH.sub.2                                                                      CN                                            38  NH.sub.2   NHCH.sub.2CH.sub.2N(CH.sub.3).sub.2                                                              CN                                            39  NH.sub.2   NHCH.sub.2CH.sub.2N(C.sub.2 H.sub.5).sub.2                                                       CN               125-129                      40  NH.sub.2   NH(CH.sub.2).sub.3OH                                                                             CN               171-172                      41  NH.sub.2   NH(CH.sub.2).sub.3OCH.sub.3                                                                      CN                                            42  NH.sub.2   NH(CH.sub.2).sub.3OC.sub.2 H.sub.5                                                               CN                                            43  NH.sub.2   NH(CH.sub.2).sub.3O-n-C.sub.3 H.sub.7                                                            CN                                            44  NH.sub.2   NH(CH.sub.2).sub.3OC.sub.6 H.sub.5                                                               CN                                            45  NH.sub.2   NH(CH.sub.2).sub.3OCH.sub.2 C.sub.6 H.sub.5                                                      CN                                            46  NH.sub.2   NH(CH.sub.2).sub.3O(CH.sub.2).sub.2OC.sub.6 H.sub.5                                              CN                                            47  NH.sub.2   NH(CH.sub.2).sub.3NH.sub.2                                                                       CN                                            48  NH.sub.2   NH(CH.sub.2).sub.3N(CH.sub.3).sub.2                                                              CN                                            49  NH.sub.2   NH(CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2                                                       CN                                            50  NH.sub.2   NHC.sub.6 H.sub.5 CN                                            51  NH.sub.2   NHCH.sub.2 C.sub.6 H.sub.5                                                                       CN                                            52  NH.sub.2   NHCH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              CN                                            53  NH.sub.2   NHCH.sub.2 (CH.sub.3)C.sub.6 H.sub.5                                                             CN                                            54  NH.sub.2   NH-cyclo-C.sub.3 H.sub.5                                                                         CN                                            55  NH.sub.2   NH-cyclo-C.sub.4 H.sub.7                                                                         CN                                            56  NH.sub.2   NH-cyclo-C.sub.5 H.sub.9                                                                         CN                                            57  NH.sub.2   NH-cyclo-C.sub.6 H.sub.11                                                                        CN                                            58  NH.sub.2   NH-cyclo-C.sub.7 H.sub.13                                                                        CN                                            59  NH.sub.2   NH-cyclo-C.sub.8 H.sub.15                                                                        CN                                            60  NH.sub.2   NHCH.sub.2CH.sub.2SCH.sub.3                                                                      CN                                            61  NH.sub.2   NHCH.sub.2CH.sub.2SC.sub.2 H.sub.5                                                               CN                                            62  NH.sub.2   NH(CH.sub.2).sub.3 SCH.sub.3                                                                     CN                                            63  NH.sub.2   NH(CH.sub.2).sub.3 SC.sub.2 H.sub.5                                                              CN                                            64  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-CH.sub.3                                                                  CN                                            65  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-CH.sub.3                                                                  CN                                            66  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-CH.sub.3                                                                  CN                                            67  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-C.sub.2 H.sub.5                                                           CN                                            68  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-C.sub.2 H.sub.5                                                           CN                                            69  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-C.sub.2 H.sub.5                                                           CN                                            70  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-OH                                                                        CN                                            71  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-OH                                                                        CN                                            72  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-OH                                                                        CN                                            73  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-Cl                                                                        CN                                            74  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-Cl                                                                        CN                                            75  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-Cl                                                                        CN                                            76  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-OCH.sub.3                                                                 CN                                            77  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-OCH.sub.3                                                                 CN                                            78  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-OCH.sub.3                                                                 CN                                            79  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-OC.sub.2 H.sub.5                                                          CN                                            80  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-OC.sub.2 H.sub.5                                                          CN                                            81  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-OC.sub.2 H.sub.5                                                          CN                                            82  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-NH.sub.2                                                                  CN                                            83  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-NH.sub.2                                                                  CN                                            84  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-NH.sub.2                                                                  CN                                            85  NH.sub.2   NHC.sub.6 H.sub.3 -(2,3)-(CH.sub.3).sub.2                                                        CN                                            86  NH.sub.2   NHC.sub.6 H.sub.3 -(2,4)-(CH.sub.3).sub.2                                                        CN                                            87  NH.sub.2   NHC.sub.6 H.sub.3 -(2,5)-(CH.sub.3).sub.2                                                        CN                                            88  NH.sub.2   NHC.sub.6 H.sub.3 -(2,6)-(CH.sub.3).sub.2                                                        CN                                            89  NH.sub.2   NHC.sub.6 H.sub.3 -(3,4)-(CH.sub.3).sub.2                                                        CN                                            90  NH.sub.2   NHC.sub.6 H.sub.3 -(3,5)-(CH.sub.3).sub.2                                                        CN                                            91  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-N(CH.sub.3).sub.2                                                         CN                                            92  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-N(CH.sub.3).sub.2                                                         CN                                            93  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-N(CH.sub.3).sub.2                                                         CN                                            94  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-CN                                                                        CN                                            95  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-CN                                                                        CN                                            96  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-CN                                                                        CN                                            97  NH.sub.2   NHC.sub.6 H.sub.4 -(2)-COOH                                                                      CN                                            98  NH.sub.2   NHC.sub.6 H.sub.4 -(3)-COOH                                                                      CN                                            99  NH.sub.2   NHC.sub.6 H.sub.4 -(4)-COOH                                                                      CN                                            100 NH.sub.2   NHC.sub.6 H.sub.4 -(2)-COCH.sub.3                                                                CN                                            101 NH.sub.2   NHC.sub.6 H.sub.4 -(3)-COCH.sub.3                                                                CN                                            102 NH.sub.2   NHC.sub.6 H.sub.4 -(4)-COCH.sub.3                                                                CN                                            103 NH.sub.2   NHC.sub.6 H.sub.4 -(2,3)-Cl.sub.2                                                                CN                                            104 NH.sub.2   NH-pyrid-2-yl     CN                                            105 NH.sub.2   NH-pyrid-3-yl     CN                                            106 NH.sub.2   NH-pyrid-4-yl     CN                                            107 NH.sub.2   NH-thien-2-yl     CN                                            108 NH.sub.2   N(CH.sub.3).sub.2 CN                                            109 NH.sub.2   N(C.sub.2 H.sub.5).sub.2                                                                         CN                                            110 NH.sub.2   N(n-C.sub.3 H.sub.7).sub.2                                                                       CN                                            111 NH.sub.2   N(n-C.sub.4 H.sub.9).sub.2                                                                       CN                                            112 NH.sub.2   N(CH.sub.2 CHCH.sub.2).sub.2                                                                     CN                                            113 NH.sub.2   N(CH.sub.3)(C.sub.6 H.sub.5)                                                                     CN                                            114 NH.sub.2   N(C.sub.2 H.sub.5)(CH.sub.2 C.sub.6 H.sub.5)                                                     CN                                            115 NH.sub.2   N(CH.sub.3)(C.sub.6 H.sub.5)                                                                     CN                                            116 NH.sub.2   N(C.sub.2 H.sub.5)(CH.sub.2 C.sub.6 H.sub.5)                                                     CN                                            117 NH.sub.2   N(CH.sub.2 C.sub.6 H.sub.5).sub.2                                                                CN                                            118 NH.sub.2   N(CH.sub.2 CH.sub.2 OH).sub.2                                                                    CN                                            119 NH.sub.2                                                                                   ##STR19##        CN                                            120 NH.sub.2                                                                                   ##STR20##        CN                                            121 NH.sub.2                                                                                   ##STR21##        CN                                            122 NH.sub.2                                                                                   ##STR22##        CN                                            123 NH.sub.2                                                                                   ##STR23##        CN                                            124 NH.sub.2                                                                                   ##STR24##        CN                                            125 NH.sub.2                                                                                   ##STR25##        CN                                            126 NH.sub.2                                                                                   ##STR26##        CN                                            127 NH.sub.2                                                                                   ##STR27##        CN                                            128 NH.sub.2                                                                                   ##STR28##        CN                                            129 NH.sub.2                                                                                   ##STR29##        CN                                            130 NH.sub.2                                                                                   ##STR30##        CN                                            131 NH.sub.2                                                                                   ##STR31##        CN                                            132 NH.sub.2                                                                                   ##STR32##        CN                                            133 NH.sub.2                                                                                   ##STR33##        CN                                            134 NH.sub.2   NHNH.sub.2        CN                                            135 NH.sub.2   NHN(CH.sub.3).sub.2                                                                              CN                                            136 NH.sub.2   NHNHC.sub.6 H.sub.5                                                                              CN                                            137 NH.sub.2   NHNHCH.sub.3      CN                                            138 NH.sub.2   N(CH.sub.3)NHCH.sub.3                                                                            CN                                            139 NH.sub.2   NHN(C.sub.2 H.sub.5).sub.2                                                                       CN                                            140 NH.sub.2   NHN(n-C.sub.3 H.sub.7).sub.2                                                                     CN                                            141 NH.sub.2   NHN(n-C.sub.4 H.sub.9).sub.2                                                                     CN                                            142 NCHN(CH.sub.3).sub.2                                                                      N(C.sub.2 H.sub.5).sub.2                                                                         CN                                            143 NCHN(CH.sub.3).sub.2                                                                      N(CH.sub.3).sub.2 CN                                            144 NCHN(C.sub.2 H.sub.5).sub.2                                                               N(CH.sub.3).sub.2 CN                                            145 NCHN(C.sub.2 H.sub.5).sub.2                                                               N(C.sub.2 H.sub.5).sub.2                                                                         CN                                            146 NH.sub.2   NHCH.sub.3        NO.sub.2                                      147 NH.sub.2   NHC.sub.2 H.sub.5 NO.sub.2                                      148 NH.sub.2   NH-n-C.sub.3 H.sub.7                                                                             NO.sub.2                                      149 NH.sub.2   NH-iso-C.sub.3 H.sub.7                                                                           NO.sub.2                                      150 NH.sub.2   NH-n-C.sub.4 H.sub.9                                                                             NO.sub.2                                      151 NH.sub.2   NH-n-C.sub.5 H.sub.11                                                                            NO.sub.2                                      152 NH.sub.2   NH-cyclo-C.sub.3 H.sub.5                                                                         NO.sub.2                                      153 NH.sub.2   NH-cyclo-C.sub.6 H.sub.11                                                                        NO.sub.2                                      154 NH.sub.2                                                                                   ##STR34##        NO.sub.2         >315                         155 NH.sub.2                                                                                   ##STR35##        NO.sub.2                                      156 NH.sub.2                                                                                   ##STR36##        NO.sub.2                                      157 NH.sub.2                                                                                   ##STR37##        NO.sub.2         275-276                      158 NH.sub.2                                                                                   ##STR38##        NO.sub.2                                      159 NH.sub.2   NHCH.sub.3        CHNCH.sub.3                                   160 NH.sub.2   NHC.sub.2 H.sub.5 CHNC.sub.2 H.sub.5                            161 NH.sub.2   N(CH.sub.3).sub.2 CHO                                           162 NH.sub.2   N(C.sub.2 H.sub.5).sub.2                                                                         CHO                                           163 NH.sub.2   N(n-C.sub.3 H.sub.7).sub.2                                                                       CHO                                           164 NH.sub.2   N(n-C.sub.4 H.sub.9).sub.2                                                                       CHO                                           165 NH.sub.2                                                                                   ##STR39##        CHO                                           166 NH.sub.2                                                                                   ##STR40##        CHO                                           167 NH.sub.2                                                                                   ##STR41##        CHO                                           168 NH.sub.2                                                                                   ##STR42##        CHO                                           169 NH.sub.2                                                                                   ##STR43##        CHO                                           170 NH.sub.2                                                                                   ##STR44##        CHO                                           171 NH.sub.2                                                                                   ##STR45##        CHO                                           172 NH.sub.2   N(CH.sub.3).sub.2 COCH.sub.3                                    173 NH.sub.2   N(C.sub.2 H.sub.5).sub.2                                                                         COCH.sub.3                                    174 NH.sub.2   N(CH.sub.3).sub.2 COC.sub.2 H.sub.5                             175 NH.sub.2   N(C.sub.2 H.sub.5).sub.2                                                                         CO-n-C.sub.3 H.sub.7                          176 NH.sub.2   N(CH.sub.3).sub.2 CO-iso-C.sub.3 H.sub.7                        177 NH.sub.2   N(CH.sub.3).sub.2 COC.sub.6 H.sub.5                             178 NH.sub.2   N(CH.sub.3).sub.2 CHC(CN).sub.2                                 179 NH.sub.2   N(C.sub.2 H.sub.5).sub.2                                                                         CHC(CN).sub.2    107-109                      180 NH.sub.2   N(n-C.sub.3 H.sub.7).sub.2                                                                       CHC(CN).sub.2                                 181 NH.sub.2   N(n-C.sub.4 H.sub.9).sub.2                                                                       CHC(CN).sub.2                                 182 NH.sub.2                                                                                   ##STR46##        CHC(CN).sub.2                                 183 NH.sub.2                                                                                   ##STR47##        CHC(CN).sub.2    225                          184 NH.sub.2                                                                                   ##STR48##        CHC(CN).sub.2                                 185 NH.sub.2                                                                                   ##STR49##        CHC(CN).sub.2    270                          186 NH.sub.2   NHCH(C.sub.6 H.sub.5).sub.2                                                                       ##STR50##                                    187 NH.sub.2   NHCH.sub.3                                                                                        ##STR51##                                    188 NH.sub.2   NHC.sub.2 H.sub.5                                                                                 ##STR52##                                    189 NH.sub.2                                                                                   ##STR53##                                                                                        ##STR54##                                    190 NH.sub.2   N(C.sub.2 H.sub.5).sub.2                                                                          ##STR55##                                    191 NH.sub.2                                                                                   ##STR56##                                                                                        ##STR57##                                    192 NH.sub.2   NHCH.sub. 3                                                                                       ##STR58##                                    193 NH.sub.2   NHC.sub.2 H.sub.5                                                                                 ##STR59##                                    194 NH.sub.2                                                                                   ##STR60##                                                                                        ##STR61##                                    195 NH.sub.2                                                                                   ##STR62##                                                                                        ##STR63##                                    196 NH.sub.2                                                                                   ##STR64##                                                                                        ##STR65##                                    197 NH.sub.2   NHCH.sub.3                                                                                        ##STR66##                                    198 NH.sub.2   NHC.sub.2 H.sub.5 CHC(CO.sub.2 CH.sub.3).sub.2                  199 NH.sub.2   N(CH.sub.3).sub.2                                                                                 ##STR67##                                    200 NH.sub.2   NHC.sub.6 H.sub.5                                                                                 ##STR68##                                    __________________________________________________________________________ 

We claim:
 1. A diaminothiophene of Formula I: ##STR69## or tautomers thereof, wherein R¹ and R² are each hydrogen, R³ is C₁ -C₂₀ -mono- or dialkylamino, C₂ -C₁₀ -mono or dialkylamino whose alkyl is substituted and/or interrupted by one or more oxygen atoms, C₂ -C₁₂ -mono- or dialkenylamino, C₃ -C₁₂ -alkynylamino, N-(C₁ -C₅ -alkyl)-N-phenylamino, hydrazino, C₁ -C₄ -mono- or dialkylhydrazino or phenylhydrazino, and R⁴ C₁ -C₆ -alkanoyl, benzoyl, cyano, nitro or ##STR70## where T⁴ is hydrogen, C₁ -C₄ -alkyl or phenyl, and T⁵ is the radical of an active methylene compound, or hydroxyimino or N-X where X is C₁ -C₂₀ -alkyl which can be substituted and/or interrupted by one or more oxygens, substituted or unsubstituted C₃ -C₆ -alkenyl, substituted or unsubstituted C₃ -C₆ -alkynyl, substituted or unsubstituted C₃ -C₁₀ -cycloalkyl, substituted or unsubstituted phenyl, pyridyl, C₁ -C₄ -alkoxycarbonylmethyl, amino, C₁ -C₄ -dialkylamino or phenylamino. 